Alkynyl esters of alkoxybenzoic acids

ABSTRACT

Alkynyl, benzyl or phenyl, ethers and esters which are ring substituted with an oxy or a thio aliphatic chain. These ethers and esters are useful in killing and preventing the proliferation of insects by upsetting their hormonal balance.

llite States Patent [1 1 Ciiodnekar et al.

ALKYNYL ESTERS OF ALKOXYBENZOIC ACIDS Inventors: Madhukar SubrayaChodnekar, Basel; Albert Pfiffner, Pfaffhausen; Norbert Rigassi,Arlesheim; Ulrich Schwleter, Reinach; Milos Suchy, Basel, all ofSwitzerland l-loftmann-La Roche lnc., Nutley, NJ.

Filed: March 10,1971

Appl. Nos 123,060

Assignee:

US. Cl. ..260/473 R, 260/348 R, 260/348 A, 260/470,.260/5l6, 260/521 R,260/521 A, 260/609 F, 260/613 D, 424/278, 424/308,

424/337, 424/341 Int. Cl ..C07c 69/78 Field of Search ..260/473 R OTHERPUBLICATIONS Luvcn et 211., J. Am. Chem. Soc. 67 1254 (1945).

Primary ExaminerLorraine A. Weinberger Assistant Examiner-John F.Terapane Attorney-Samuel L. Welt, Jon S. Saxe, Bernard S. Leon, WilliamH. Epstein, George M. Gould and Ronald A. Schapira 5 7 ABSTRACT Alkynyl,benzyl or phenyl, ethers and esters which are ring substituted with anoxy or a thio aliphatic chain.

These ethers and esters are useful in killing and preventing theproliferation of insects by upsetting their hormonal balance.

8 Claims, No Drawings ALKYNYL ESTERS OF ALKOXYBENZOIC ACIDS SUMMARY OFTHE INVENTION In accordance with this invention, it has been found thatcompounds of the formula:

wherein R R and R are methyl or ethyl; R and R are hydrogen or methyl; Ris lower alkynyl; A, B, C, D, E and F are individually hydrogen or A andB taken together form a carbon to carbon bond or an oxygen bridge, C andD taken together form a carbon to carbon bond, and E and F takentogether form a carbon to carbon bond; 2 is oxygen or sulfur; Y and Yare hydrogen, halogen, lower alkyl or lower alkoxy; X is oxygen CH orCOO-; and m, n, and p are integers of from 0 to 1, with 1, least one ofm, n and p being 1; with the proviso that when m and n are 0, E and Fare individually hydrogen, or taken together form a carbon to carbonbond or an oxygen bridge; upset the hormone balance of pests such asinsects to prevent them from growing and reproducing.

The compounds of Formula I are prepared by reacting a compound of theformula:

wherein R R R R R,, A, B, C, D, E, F, Z, Y, Y, X, m, n and p are asabove and M is an alkali metal or, where X is oxygen, an alkali metal orhydrogen;

with an alkynyl halide of the formula:

III

wherein R1, R R R R,,, A, B, C, D, E, F, Hal, m, n

andp are as above; with a compound of the formula:

wherein R X, Y, Y and Z are as above and M is an alkali metal or, whereZ is oxygen, an alkali metal or hydrogen. The compounds of Formula I,wherein X is wherein R,, R R R R A, B, C, D, E, F, Z, Y, Y, m, n and pare as above and R is hydrogen, lower alkyl or aralkyl;

with an alcohol of the formula:

R -OH wherein R is as above. In the case where, in the compound ofFormula I, A and B taken together form a carbon to carbon bond, thiscompound can be epoxidized to a compound of Formula I wherein A and Btaken together form an oxygen bridge.

VII

DESCRIPTION OF THE PREFERRED EMBODIMENT As used throughout thisapplication, the term lower alkyl comprehends both straight-chain andbranchedchain, saturated alkyl hydrocarbon groups having from one to sixcarbon atoms, such as methyl, ethyl, propyl,

isopropy], etc. As used herein, the term lower alkoxy comprehendsloweralkyloxy groups wherein a loweralkyl is defined as above, such asmethoxy, ethoxy propoxy, etc. Similarly, as used herein, the term loweralkynyl" includes straight-chain and branched-chain,

acetylenically unsaturated hydro carbon groups having from two to sixcarbon atoms, such as ethynyl, propargyl, butynyl, etc. As also usedherein, the term halogen" or halo comprehends, when not expressly statedotherwise, all four halogens, i.e. fluorine,

chlorine, bromine and iodine. As further used herein, the term alkalimetal" comprehends the alkali metals of the first group of the periodicchart, such as sodium and potassium. As still further used herein, theterm aralkyl comprehends aryl lower alkyl groups wherein aryl"comprehends mono-nuclear aromatic hydrocarbons, such as phenyl, tolyl,etc., which can be substituted or unsubstituted in one or morepositions, and polynuclear aromatic groups, such as naphthyl,phenanthyl, etc., which can also be substituted or unsubstituted in oneor more positions, with a nitro, halo, lower alkyl or lower alkoxysubstituent, and wherein lower alkyl" is as defined above. The preferredaralkyl group is benzene.

The compounds of Formula I are useful in the control of and incombatting invertebrate animals, such as arthropods and nematodes. Thecompounds of formula I are especially useful against insects,particularly Tenebrio molitor, Tineola biselliella, Carpocapsapomanella, Leptinotarsa decemlineata, Calandra granaria, Dysdercuscingulatus and Ephestia kiz'hniella.

In contrast to most of the known pest-control agents which kill, disableor repell the pests by acting as contact-poisons and feed-poisons, thecompounds of Formula I above prevent maturation and proliferation ofthese pests by interfering with their hormonal system. In insects, forexample, the transformation to the imago, the laying of viable eggs andthe development of laid normal eggs is distrubed. Furthermore, thesequence of generations is interrupted and the insects are indirectlykilled.

The compounds of Formula I above are practically non-toxic tovertebrates. The toxicity of the compounds of Formula I is greater than,1,000 mg/kg body weight. Moreover, these compounds are readily degradedand the risk of accumulation is therefore excluded. Therefore, thesecompounds can be used without fear of danger in the control of pests inanimals; plants; foods; and textiles.

Generally, in controlling invertebrate animals, the compounds of FormulaI are applied to the material to be protected, e.g. foodstuffs, feeds,textiles, plants, in concentrations of from about to 10' gm/cm of thematerial to be protected. Generally, it is preferred to utilize thecompounds of Formula I above in a composition with a suitable inertcarrier. Any conventional inert carrier can be utilized.

The compounds of Formula I can, for example, be used in the form ofemulsions, suspensions, dusting agents, solutions or aerosols. Inspecial cases, the materials to be protected (e.g., foodstuffs, seeds,textiles and the like) can also be directly impregnated with theappropriate compound or with a solution thereof. Moreover, the compoundscan also be used in a form which only releases them by the action ofexternal influences (e.g., contact with moisture) or in the animal bodyitself. It is also possible to use the compounds in admixture with otherknown pesticides.

The compounds of Formula I above can be used as solutions suitable forspraying on the material to be protected which can be prepared bydissolving or dispersing these compounds in a solvent such as mineraloil fractions; cold tar oils; oils of vegetable or animal origins;hydrocarbons such as napthalenes; ketones such as methyl ethyl ketone;or chlorinated hydrocarbons such as tetrachloroethylene,tetrachlorobenzene, and the like. Such sprays suitably have aconcentration of the compound of Formula I of 0.01 to 5 percent byweight, with a concentration of 0.1 percent being preferred. Thecompounds of Formula I above can also be prepared in forms suitable fordilution with water to form aqueous liquids such as, for example,emulsion concentrates, pastes or powders. The compounds of Formula Iabove can be combined with solid carriers for making, dusting orstrewing powders as, for example, talc, kaolin, bentonite, calciumcarbonate, calcium phosphate, etc. The compositions containing thecompounds of Formula I above can contain, if desired, emulsifiers,dispersing agents, wetting agents, or other active substances such asfungicides, bacteriacides, nematocides, fertilizers and the like. Thematerials which are to be protected act as bait for the insect. In thismanner, the insect, by contacting the material impregnated with acompound of Formula I above, also contacts the compound itself.

In accordance with this invention, representative examples of thepreferred compounds of Formula I are as follows:

acid

pargyl ester;

p-[ (4,S-epoxy-l ,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

p-[( l-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid propargyl ester;

p-[(6,7-epoxy-3,7-dimethyl-2-octenyl)oxy]benzoic acid propargyl ester;

p-[ 2,3-epoxy-3-methylbutyl )oxyl-a-propargloxytoluene;

I 2,3-epoxy-3-methylbutyl)oxy]-4-propargyloxybenzene;

p-[(3,7,1 I-trimethyl-dodeca-2,6,l0-trienyl)oxylbenzoic acid propargylester;

p-[ 1,5-dimethyl-4-hexenyl)oxy]benzoic acid propargyl ester;

p-[( 1 ,5-dimethylhexyl)thio]-a-propargyloxytoluene;

l-[( l,5-dimethylhexy1)oxy]-4-(propargyloxy)benzene;

p-[( I ,S-dimethylhexyl)oxy]benzoic acid propargyl ester;

4-[ l ,5-dimethylhexyl)oxyl-a-(propargyloxy)toluene;

p-[(4,5-epoxy-l,5-dimethylhexyl)oxylbenzoic acid propargyl ester;

p-[ 1 ,S-dimethylhexyl )oxy]benzoic acid-2-pentynyl ester;

p-[( l ,4,5-trimethylhexyl)oxy]benzoic acid propargyl ester;

p-[( l ,S-dimethylhexyl)thio]benzoic acid propargyl ester;

p-[ 3 ,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid propargyl ester;

p-[(3,6,7-trimethyloctyl)oxy]benzoic acid propargyl ester;

4-[( l,S-dimethylhexyl)oxy]-3-chlorobenzoic propargyl ester;

p-[(l,5-dimethylhexyl)oxy]vanillic acid propargyl ester;

3-methyl-4-[(3,7-dimethylocta-2,6-dienyl)oxy ]benzoic acid propargylester;

3-bromo-4-[(6,7-dimethyI-2,6-octadienyl)oxy]-5- methoxy-benzoic acidpropargyl ester; and

4-[ 3 ,7-dimethyl-2,6-octadienyl )oxy]-3 ,S-dimethoxy-benzoic acidpropargyl ester.

acid

Especially preferred are the compounds of Formula I having the formula:

wherein R R R,,, A, B, X, Y, Y and Z are as above. Particularlypreferred are the compounds of formula Ia wherein Z is oxygen, Y ishydrogen, and A and B individually are hydrogen or taken together forman oxygen bridge. Quite particularly preferred are the followingcompounds of Formula Ia: l-[( 1,S-dimethylhexyl)oxy]-4-propargyloxybenzene;

p-[( l,5-dimethylhexyl)oxy]benzoic acid propargyl ester;

4-[( 1,5-dimethylhexyl)oxy]-a-(propargyloxy)toluene;

p-[(4,5-epoxy-1,5-dimethylhexyl)oxylbenzoic acidpropargyl ester; and

p-[( l ,4,5-trimethylhexyl)oxy]benzoic acid propargyl ester.

Also especially preferred are the compounds of Formula I having theformula:

wherein R R R A, B, E, F, X, Y, Y and Z are as above.

Further especially preferred compounds are the compounds of Formula Iwherein R R and/or R are methyl; R and/or R is hydrogen; Z is oxygen,and/or Y and Y are hydrogen.

One method for preparing the compounds of Formula I involves reacting,in a well known manner, a compound of Formula II with the alkynyl halideof Formula III. This reaction is suitably conducted in an inert solventand preferably in the presence of an aprotonic solvent. In carrying outthis reaction, any conventional inert organic solvent can be utilized,with benzene, toluene, dioxane, 1,2-dimethoxymethane and tetrahydrofuranbeing preferred and tetrahydrofuran being especially preferred. In thisreaction, any conventional aprotonic solvent may be utilized, withhexamethyl phosphoric acid triamide being preferred. In

this reaction, temperature and pressure are not critical, and thereaction can be suitably carried out in a temperature range of 0C. tothe boiling point of the reaction mixture. In a preferred embodiment ofthis reaction, the reaction is carried out at ca 70C., the refluxtemperature of the especially preferred solvent.

Another method for preparing the compounds of Formula I involvesreacting, in a well known manner, the compounds of Formulas IV and V.This reaction is also suitably carried out in an inert solvent,preferably in the presence of an aprotonic solvent. In carrying out thisreaction, any conventional inert organic solvent can be utilized, withbenzene, toluene, dioxane, 1,2- dimethoxymethane and tetrahydrofuranbeing preferred and tetrahydrofuran being especially preferred. In thisreaction, any conventional aprotonic solvent may be utilized, withhexamethyl phosphoric acid triamide being preferred. In this reaction,temperature and pressure are not critical, and the reaction can besuitably carried out in a temperature range of 0C. to the boiling pointof the reaction mixture. In a preferred embodiment of this reaction, asin the above reaction, the preferred temperature is ca C.

The reaction mixtures from the reactions of either a compound of FormulaII with a compound of Formula III or a compound of the Formula IV with acompound of Formula V can be worked up in a conventional manner toobtain the compounds of Formula I. A preferred method of working upincludes: pouring the reaction mixture onto ice; extracting the compoundof Formula I with a conventional inert organic solvent, preferablydiethyl ether; washing the solvent extract with water; drying thesolvent and evaporating the solvent. The residual compound of Formula Ican be further purified by adsorption, preferably on Kieselgel oraluminum oxide.

The above reactions of a compound of Formula II, wherein M is hydrogen,with an alkynyl halide of Formula III and of a compound of Formula V,wherein M signifies hydrogen, with a compound of Formula IV areexpediently effected in the presence of an acid binding agent. In thesereactions, any conventional acid binding agent may be utilized. Thepreferred acid binding agents are the carbonates and organic bases, suchas pyridine, triethylamine and quinoline, with the carbonates beingespecially preferred, particularly potassium carbonate. Further, inthese reactions, wherein M of the compound of Formula II and M of thecompound of Formula V are hydrogen, the preferred solvents are acetoneand methyl ethyl ketone.

Still another method for preparing the compounds of Formula I, involvesthe esterification of an acid of the compound of Formula VI where R ishydrogen with an alcohol of Formula VII. In carrying out this reaction,the acid is expediently converted, initially, in an inert solvent and inthe presence of an acid binding agent into the corresponding acid halideby treatment with a halogenating agent. In this reaction, anyconventional inert organic solvent can be used, with petroleum ether,benzene and hexane being preferred solvents. Also, in this reaction, anyconventional acid binding agent, such as the organic bases, can be used,with pyridine, triethylamine, and quinoline being preferred and pyridinebeing especially preferred. Further, in this reaction, any conventionalhalogenating agent such as thionyl chloride, phosphorus trichloride,thionyl bro mide, and phosphorous oxychloride can be used, with thionylchloride being preferred. In this reaction, temperature and pressure arenot critical, and the reaction may be suitably carried out at roomtemperature (25C.).

The resulting acid halide and the alkynyl alcohol of Formula VII arethen reacted in an inert solvent and in the presence of an acid bindingagent. In this reaction, any conventional inert organic solvent can beutilized with benzene, toluene, hexane, iso-octane, chloroform, carbontetrachloride and ethylene glycol dimethyl ether being preferredsolvents. Also in this reaction, any conventional acid binding agent maybe utilized,

with the organic bases, such as pyridine, triethylamine, and quinolinebeing preferred and pyridine being especially preferred. In carrying outthis reaction, temperature and pressure are not critical, and thereaction can be suitably carried out at room temperature.

Still another method for preparing the compounds of Formula I involvesthe trans-esterification of a compound of Formula VI wherein R is alkylor aralkyl utilizing an alcohol of Formula VII. This reaction isexpediently effected in an excess of the alcohol, in which case thisalcohol can also serve as the solvent. However, the reaction can also beconducted in an inert organic solvent, any conventional inert organicsolvent being suitable and the hydrocarbons, particularly benzene andtoluene, being preferred. Temperature and pressure are not critical tothis reaction, and the reaction can be expediently carried out in atemperature range between room temperature and the reflux temperature ofthe reaction mixture, with the reflux temperature being preferred. Thisreaction is preferably carried out in the presence of a catalyst such assodium, sodium methoxide, or p-toluene-sulphonic acid.

The epoxidation of a compound of Formula I wherein M is 1, Z is oxygen,and A and B taken together form a carbon to carbon bond can expedientlybe carried out by treating the compound in an inert solvent with aperacid. In carrying out this reaction, any conventional inert organicsolvent may be utilized with the halogenated hydrocarbons such asmethylene chloride or chloroform being preferred. Any conventionalperacid may be utilized in this reaction. Among the preferred peracidsare perbenzoic acid, peracetic acid, pertungstic acid, performic acid,m-chloroperbenzoic acid and perphthalic acid, with m-chloroperbenzoicacid being especially preferred. In carrying out this reaction,temperature and pressure are not critical, the preferred temperaturerange being lC. to room temperature.

Another method for epoxidizing the compound of Formula I, where M is I,wherein Z is oxygen or sulfur, and A and B taken together form a carbonto carbon bond, involves first treating the compound with water and anN-halosuccinimide, halo" being chlorine, bromine, or iodine, withN-bromosuccinimide being preferred, to obtain a halohydrin of theformula:

wherein R R R R R R C, D, E, F, X, Y, Y Z, n and p are as above, and Halis chlorine, bromine or iodine. In this reaction, temperature andpressure are not critical, the reaction being preferably carried outbetween 0C. and 25C. In carrying out this reaction, the unsaturatedcompound of fonnula I is preferably initially suspended in water. Thenan inert organic solvent is added to the suspension to give ahomogeneous concentrated solution of the compound of Formula I in waterand organic It: in

solvent. Any conventional inert organic solvent can be utilized in thisreaction, dioxane, tetrahydrofuran and 1,2-dimethoxyethane beingpreferred. The N-halosuccinimide is then introduced portionwise intothis homogeneous solution to yield the halohydrin of Formula VIII.

These halohydrins can then be converted by the action of a base to thecorresponding epoxide. In carrying out this reaction, any conventionalbase is suitable, with the alkali metal alkanolates being preferred,especially sodium methylate in methanol. In this reaction, temperatureand pressure are not critical, the reaction being preferably carried outbetween 0C. and 25C. Any conventional inert organic solvent can beutilized in this reaction, dioxane, tetrahydrofuran and 1,2-dimethoxymethane being preferred.

The compounds of Formulas II and VI can be obtained by first reacting acompound of Formula IV with a compound of the formula:

wherein R,, R R R R R A-F, Y, Y', Z, m, n

and p are as above. The compound of Formula X, wherein R is formyl orCOOR is then reduced to a compound of the formula:

wherein R R R R R A-F, Y, Y, Z, m, n and p are as above and R' isCI-I,OH. Alternatively, the compound of Formula X, wherein R is --COOR,,is then saponified or the compound of Formula X, wherein R is formyl, isthen oxidized to a compound of the formula:

7 l l H -4 n x wherein R,, R R R R A-F, Y, Y, 2, m, n and p are as aboveand R",, is --COOI I.

The compound ofFormula X, wherein R is forrnyl or -COOR,, can beconverted to the compound of formula XI, wherein R' is -CI'I,OI-I, byreduction. This reduction reaction can be carried out in a conventionalmanner with a metal hydride, such as an alkali metal hydride, in aninert organic solvent. In carrying out this reaction, any conventionalmetal hydride can be used, with the preferred hydrides being mixed metalhydrides, particularly sodium borohydride or lithium aluminum hydride,and alkylated metal hydrides, particularly, dialkyl aluminum hydrides.Especially preferred hydrides are di-isobutyl aluminum hydride andbis-(methoxy-ethyleneoxy) sodium aluminum hydride. In this reaction, anyconventional, inert organic solvent can be used, with the preferredsolvents being: the alkanols, especially methanol, in the presence ofsodium borohydride; the ethers, especially tetrahydrofuran or dioxane,in the presence of lithium aluminum hydride; and the ethers and thehydrocarbons, especially hexane, benzene or toluene, with the alkylatedmetal hydrides, particularly di-isobutyl aluminum hydride. Also, incarrying out this reaction, temperature and pressure are not critical,with a temperature range of -C to 50C. being preferred.

The compound of Formula X, wherein R is COOR can be converted to thecompound of Formula XII, wherein R is --COOII, by saponification. Thissaponification reaction can be carried out in a conventional mannerusing an alkali metal hydroxide, such as sodium or potassium hydroxide.In carrying out this reaction, temperature and pressure are notcritical, and the reaction can be carried out at elevated temperature.In this reaction, any conventional inert solvent which dissolves boththe alkali metal hydroxide and the compound of formula X may be utilizedwith diethylene glycol/water or methanol/water (lzl) being preferred.

The compound of Formula X, wherein R is formyl, can be converted to thecompound of Formula XII, wherein R"; is ,COOI-I, by oxidation. Thisoxidation reaction can be carried out in a conventional manner usingsilver oxide. In carrying out this reaction, temperature and pressureare not critical, and the reaction can be carried out at roomtemperature. The silver oxide, preferably Ag,0, is preferably formed insitu in an aqueous solution of silver nitrate and caustic soda (NaOI-I).This reaction is carried out in water or in an organic solvent misciblewithwater. Any conventional organic solvent miscible with water may beused, with the following solvents being preferred: the lower alcohols,particularly methanol, ethanol and isopropanol; the ethers,particularly, 1,4-dioxane; and the ether alcohols, particularly2-methoxy-ethanol and Z-ethoxyethanol.

When the compounds of Formulas X, XI, and XII, wherein Z is oxygen, areunsaturated, they can, if desired, be hydrogenated in a conventionalmanner by, for example, hydrogenating in the presence of a conventionalhydrogenation catalyst. In carrying out this reaction, temperature andpressure are not critical, a temperature range between about C. and theboiling temperature of the reaction mixture and atmospheric or elevatedpressures being preferred. Suitable as hydrogenation catalysts are, forexample, Raney-nickel or preferably the noble metals, with palladium andplatinum being especially preferred. Suitable as solvents are aceticacid ethyl ester and the alkanols such as methanol and ethanol.

When the compounds of Formulas X, XI, and XII, are unsaturated, theycan, if desired, be epoxidized in the same manner described above forthe epoxidation of the compounds of Formula I.

The compounds of Formula X, wherein R is hydroxy or hydroxymethyl, ofFormula XI wherein R, is CH OI-I and of Formula XII, wherein R"; isCOOH, can be directly converted to the alkali metal salt of Formula II.This reaction can be expediently effected by treatment with an alkalimetal hydride, alkali metal alcoholate or an alkali metal hydroxide,sodium being the preferred alkali metal. This reaction is preferablycarried out in the presence of an inert organic solvent. Anyconventional inert organic solvent may be utilized, with dioxane,tetrahydrofuran, dimethylformamide or diethyl ether being the preferredsolvents with an alkali metal hydride, with a lower alkanol, especiallymethanol, being the preferred solvent with an alkali metal alcoholate,and with methanol, ethanol, acetone or the like being the preferredsolvent with an alkali metal hydroxide.

In the species of the compounds of Formulas I, II, IV, VI, X, XI and XIIof this invention, wherein the sidechain is unsaturated or epoxidized,these species exist as a cis/trans isomer mixture. The isomer mixturecan be separated into the all cis or all trans isomers in a conventionalmanner by, for example, gas chromatography.

By this method, the isomer mixture is dissolved in an inert organicsolvent, hexane, diethyl ether or acetic acid ethyl ester beingpreferred solvents, and then adsorbed on Kieselgel. The isomers adsorbedin different zones can be eluted with one of the aforesaid solvents orsolvent mixtures and isolated.

The isomer mixtures can, in individual cases, also be separated byfractional distillation methods or possibly also be fractionalcrystallization methods.

The following examples illustrate the invention. All temperatures arestated in degrees centrigrade. The inert gas atmosphere is nitrogen. Theterm hexane/l5 acetic ester as used in Examples 5 and 41 encompasses asolution consisting of 85 percent hexane and 15 percent ethyl acetate(by volume). The term bis(2-methoxy-ethoxy) sodium aluminum hydride asused in Example 27 comprehends a benzenic solution of 70 percent byweight of bis(2-methoxy-ethoxy)sodium aluminum hydride. The term byweight mchlorperbenzoic acid as used in Examples 31, 35 and 34 meansthat the m-chlorperbenzoic acid contains 20 percent m-chlorbenzoic acidand that the percentage of m-chlorperbenzoic acid present in the mixturewas determined by titration in the usual manner.

EXAMPLE 1 l 1.8 g of a 50 percent by weight suspension of sodium hydridein mineral oil is washed twice in an inert gas atmosphere with 50 ml oftetrahydrofuran each time and then added to 150 ml of tetrahydrofuran. Asolution of 36.5 g of hydroquinone monopropargyl ether dissolved in 80ml of tetrahydrofuran is then added dropwise to the sodium hydridemixture. 47.5 g of 2- bromo-6-methylheptane in 80 ml of hexamethylphosphoric acid triamide is subsequently added dropwise to the mixture.The reaction mixture is heated under reflux conditions for 2 hours, thencooled, poured onto ice and exhaustively extracted with diethyl ether.The ether extract is washed with water, dried over sodium sulfate andevaporated under reduced pressure. The residual, oily,l-[(l,5-dimethylhexyl) oxyl-4-(propargyloxy)-benzene is purified byadsorption on Kieselgel; B.P. l50l52C/l mmHg.

EXAMPLE 2 By utilizing the procedure of Example 1, by reactinghydroquinone monopropargyl ether with 3-methyl-2- butenyl bromide, thereis obtained 1-[(3-methyl-2-butenyl)oxy]-4-propargyloxy-benzene; B.P.l45-l48 C/1 mmHg.

EXAMPLE 3 By utilizing the procedure of Example 1 by reacting syringicacid propargyl ester with geranyl bromide, there is obtained4-[(3,7-dimethyl-2,6-octadienyl)oxy]-3,5-dimethoxy benzoic acidpropargyl ester; u 1.5320

EXAMPLE 4 By utilizing the procedure of Example 1, by reactingS-bromovanillic acid propargyl ester and geranyl bromide, there isobtained 3-bromo-4-[(6,7-dimethyl-2,6- octadienyl)oxy]-5-methoxy-benzoicacid propargyl ester; n 1.5440.

EXAMPLE 5 43.5 g. of a 50 percent by weight suspension of sodium hydridein mineral oil is washed twice in an inert gas atmosphere with 100 ml oftetrahydrofuran each time and then added to 150 ml of tetrahydrofuran. Asolution of 100 g. of hydroquinone in 100 ml of tetrahydrofuran is addeddropwise to the sodium hydride mixture. 108 g. of propargyl bromide in150 ml of hexamethyl phosphoric acid trinmide is subsequently addeddropwise to the mixture. The reaction mixture is heated under refluxconditions for 2 hours, then cooled, poured onto ice and exhaustivelyextracted with diethyl ether. The ether extract is washed with water,dried over sodium sulfate and evaporated under reduced pressure. Theresidual mixture is separated by chromatography on Kieselgel.Hydroquinone dipropargyl ether is eluted with percent acetic ester. M.P.50C. With hexane/% acetic ester there is eluted hydroquinonemonopropargyl ether. B.P. l00-l02C/1.0 mml-lg.

EXAMPLE 6 By utilizing the procedure of Example 5, by reacting syringicacid and propargyl bromide, there is obtained syringic acid propargylester, F. P. l05l06C.

EXAMPLE 7 By utilizing the procedure of Example 5, by reactingS-bromovanillic acid with propargyl bromide, there is obtainedS-bromovanillic acid propargyl ester; M.P. 12l-122C.

EXAMPLE 8 4.0 g. of a 50 percent by weight suspension of sodium hydridein mineral oil is washed twice in an inert gas atmosphere with 25 ml oftetrahydrofuran each time and then, added to ml of tetrahydrofuran. Asolution of 20.6 g of p-[(l,S-dimethylhexyl)oxylbenzoic acid in 100 mlof tetrahydrofuran is then added dropwise to the sodium hydride mixture.Ten g of propargyl bromide in 40 ml of hexamethyl phosphoric acidtriamide is subsequently added dropwise to the mixture. The reactionmixture is heated under reflux conditions for 2 hours, then cooledpoured onto ice and exhaustively extracted with diethyl ether. The etherextract is washed with water, dried over sodium sulfate and evaporatedunder reduced pressure. The residual oilyp-[(l,S-dimethylhexyl)oxylbenzoic acid propargyl ester is purified byadsorption of Kieselgel; B.P. 207-2l0l mm Hg.

EXAMPLE 9 By utilizing the procedure of Example 8, by reactingp-famesyloxybenzoic acid with propargyl bromide, there is obtainedp-farnesyloxybenzoic acid propargyl ester; B.P. 245-250C/0.l mm Hg.

EXAMPLE 10 By utilizing the procedure of Example 8, by reacting p-[( l,5-dimethyl-4-hexenyl)oxy]benzoic acid with propargyl bromide, there isobtained p-[(1,5-dimethyl-4- hexenyl)oxy]benzoic acid propargyl ester; n1.5252.

EXAMPLE ll By utilizing the procedure of Example 8, by reacting p-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid with propargyl bromide,there is obtained p-[(3,7-dimethyl- 2,6-octadienyl)oxy]benzoic acidpropargyl ester; B.P. 137C/0.0l mml-lg.

EXAMPLE 12 By utilizing the procedure of Example 8, by reactingp-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid with propargylbromide, there is obtained p-[(3,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid propargyl ester; n,,= 1.5349.

EXAMPLE 13 By utilizing the procedure of Example 8, by reacting p-[( l,S-dimethylhexyl)oxy]-3-chlorobenzoic acid with propargyl bromide, thereis obtained 4-[( 1,5-dimethylhexyl)oxy]-3-chlorobenzoic acid propargylester; n 1.5155.

EXAMPLE l4 By utilizing the procedure of Example 8, by reacting3-methoxy-4-( 1,5-dimethylhexyloxy)-benzoic acid with propargyl bromide,there is obtained 3-methoxy- 4-( l ,5-dimethylhexyloxy)-benzoic acidester; n 1.5151.

propargyl EXAMPLE 15 By utilizing the procedure of Example 8, byreacting 5 p-[(1,4,5-trimethylhexyl)oxylbenzoic acid with propargylbromide, there is obtained p-[(1,4,5-trimethylhexyl)oxy]benzoic acidpropargyl ester; n 1.5050.

EXAMPLE 16 EXAMPLE 17 By utilizing the procedure of Example 8, byreacting p-[( 1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid withpropargyl bromide, there is obtained p-[(1-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid propargyl ester; 11,, 1.5200. 1

EXAMPLE 18 By utilizing the procedure of Example 8, by reacting3-methyl-4-[(3,7-dimethylocta-2,6-octadieny1)-oxy]- benzoic acid withpropargyl bromide, there is obtained 3 -methyl-4-[ (3 ,7-dimethyl-octa-2,6-dienyl )oxy] benzoic acid propargyl ester; n,,= 1.5331.

EXAMPLE 19 13.7 g of a 50 percent suspension of sodium hydride inmineral oil is washed twice in an inert gas atmosphere with 70 ml oftetrahydrofuran each time and then, added to 100 ml of tetrahydrofuran.A solution of 40 g of p-hydroxybenzoic acid methyl ester in 250 ml oftetrahydrofuran is then added dropwise to the sodium hydride mixture. 50g of 2-bromo-6-methylhept-5-ene in 80 ml of hexamethyl phosphoric acidtriamide is subsequently added dropwise to the mixture. The reactionmixture is heated under reflux conditions for 2 hours, poured onto iceand exhaustively extracted with diethyl ether. The ether extract iswashed with water, dried over sodium sulfate and evaporated underreduced pressure. The residual oilyp-[(1,5-dimethyl-4-hexenyl)oxy]benzoic acid methyl ester is purified byadsorption on Kieselgel; n 1.5 109.

EXAMPLE 20 By utilizing the procedure of Example 19, by reactingp-hydroxybenzoic acid methyl ester with 2'bromo- 6-methyl heptane, thereis obtained p-[(l,5-dimethylhexyl)oxy]benzoic acid methyl ester; B.P.132l34 C/.l mmlllg.

EXAMPLE 21 By utilizing the procedure of Example 19, by reactingp-hydroxybenzoic acid methyl ester with 2-bromo- 5,6-dimethyl heptane,there is obtained p-[(1,4,5- trimethylhexyl)oxy]benzoic acid methylester; n 1.4938.

EXAMPLE 22 By utilizing the procedure of Example 19, by reactingp-hydroxybenzoic acid methyl ester with 3-bromo- 7-methylnon-6-ene,there is obtained p-[(1-ethyl-5- methyl-4-heptenyl)oxy]benzoic acidmethyl ester; B.P. 202205C/l2 mml-lg.

EXAMPLE 23 By utilizing the procedure of Example 19, by reacting3-methyl-4-hydroxybenzoic acid methyl ester with l-bromo-3,7dimethyl-2,6-octadiene, there is obtained 3 -methyl-4- 3 ,7-dimethyl-2,6-octadienyl )oxy benzoic acid methyl ester; n 1.5248.

EXAMPLE 24 7.2 g of p-[( l,5-dimethyl-hex-4-enyl)oxyI-benzoic acidmethyl ester is dissolved in ml of 2-N aqueous caustic soda, dilutedwith ml of an aqueous solution of 50 percent by volume methanol andheated under reflux for 1% hours. The reaction solution is then cooled,treated with 200 ml of water and exhaustively extracted with diethyl'ether. The alkaline aqueous phase is acidified with 2-N hydrochloricacid and exhaustively extracted with diethyl ether. The latter etherextract is dried over sodium sulfate and evaporated under reducedpressure. The residual p-[( 1 ,S dimethylhex-4-enyl)oxy]benzoic acid ispurified by crystallization from benzene; M.P. 5759C.

EXAMPLE 25 By utilizing the procedure of Example 24, the following acidscan be obtained from their corresponding methyl esters:

p-[(1,S-dimethylhexyl)oxylbenzoic acid; MP. C;

p-[ (3 ,7,1 1-trimethy]-dodeca-2,6,10-trienyl)oxy]benzoic acid; M.P.81C.;

p-[ 3 ,7-dimethyl-2,6-octadienyl )oxy ]benzoic acid; M.P. 118-l20C.;

p-[ 3 ,6,7-trimethylocta-2,6-dienyl)oxy]benzoic acid; MP. 128129C.;

p-[( 1 ,S-dimethylhexyl)oxy]-3-chlorobenzoic acid; n 1.5231;

p-[( l ,5 -dimethylhexyl )oxy ]vanillic acid; MP. 69-70C.;

p-[ 3-methyl-2-butenyl)oxy]benzoic acid; MP.

p-[( l ,4,5-trimethylhexyl)oxylbenzoic acid; n l .508 2;

p-[( l-ethyl-5-methyl-4-heptenyl)oxy]benzoic acid; n21 =l.4891; and

3-methyl-4-[ 3 ,7-dimethyl-2,6-octadienyl)oxy ]benzoic acid; EP. 93-94C.

EXAMPLE 26 cooled, poured onto ice and exhaustively extracted withdiethyl ether. The ether extract is washed with water, dried over sodiumsulfate and evaporated under reduced pressure. The residual oilyp-[(l,5-dimethylhexyl)oxy]-a-propargyloxy-toluene is purified byadsorption of Kieselgel; B.P. 170175C/1 .0 mmHg.

EXAMPLE 27 Forty-two g of p-[(1,S-dimethylhexyl)oxy]benzoic acid methylester is dissolved in 250 ml of benzene and, with stirring, treateddropwise with 50 g of 70 percent bis(2-methoxy-ethoxy)sodium aluminumhydride. The reaction solution is further stirred at 25C. for hours andthereafter treated with water. The organic phase is separated off, driedunder sodium sulfate, carefully filtered (using a filter aid) andevaporated under reduced pressure. There is obtained a residual of p-[(l ,5- dimethylhexyl)oxy]benzyl alcohol; B.P. 180182 C/1.0 mmI-lg.

EXAMPLE 28 By utilizing the procedure of Example 26, by reactionp-[(3-methyl-2-butenyl)oxylbenzyl alcohol with propargyl bromide, thereis obtained 1-[(3-methyl-2- butenyl)oxy]-4-propargyloxy-toluene; B.P.146149 C/1 mmHg.

EXAMPLE 29 10.1 g of a 50 percent by weight suspension of sodium hydridein mineral oil is washed twice in an inert gas atmosphere with 50 ml oftetrahydrofuran each time and then, introduced into 100 ml oftetrahydrofuran. A solution of 32 g of p-hydroxybenzoic acid methylester in 200 ml of tetrahydrofuran is then added dropwise to the sodiumhydride mixture. 40.5 g of 1-bromo-3- methylbut-Z-ene in 80 ml ofhexamethyl phosphoric acid triamide is subsequently added dropwise tothe mixture. The reaction mixture is heated under reflux conditions for2 hours, then cooled, poured onto ice and exhaustively extracted withdiethyl ether. The ether extract is washed with water, dried over sodiumsulfate and evaporated under reduced pressure. The residual oilyp-[(3-methyl-2-butenyl)oxy]benzoic acid methyl ester is purified byadsorption on Kieselgel. M.P. 4546C.

By utilizing the procedure of Example 27, p-[(3-methyl-2-butenyl)oxy]benzoic acid methyl ester is converted intop-[(3-methyl-2-butenyl)oxy]benzyl alcohol; M.P. 4l42C.

EXAMPLE 30 2.2 g of 50 percent by weight suspension of sodium hydride inmineral oil is washed twice in an inert gas atmosphere with 25 ml oftetrahydrofuran each time and then added to 30 ml of tetrahydrofuran asolution of 9.9 g of p-[(2,3-epoxy-3-methylbutyl)oxy]benzoic acid in 100ml of tetrahydrofuran is then added dropwise to the sodium hydridemixture 5.5 g of propargyl bromide in 20 ml of hexamethyl phosphoricacid triamide is subsequently added dropwise to the mixture. Thereaction mixture is heated under reflux conditions for 2 hours, thencooled, poured onto ice and exhaustively extracted with diethyl ether.The ether extract is washed with water, dried over sodium sulfate andevaporated under reduced pressure. The residual oily p-[(2,3-epoxy-3-methylbutyl)oxylbenzoic acid propargyl ester is purified byadsorption on Kieselgel; M.P. -81C.

EXAMPLE 31 3.9 g of p-[(1,5-dimethyl-hex-4-enyl)oxy]benzoic acidpropargyl ester is dissolved in 150 ml of methylene chloride. Thesolution is treated dropwise at 0C. with a solution of 3.0 g of 80percent by weight mchloroperbenzoic acid in ml of methylene chloride.After 15 mins., the reaction mixture is successively washed with anaqueous solution of 2 percent by weight sodium bisulphite with anaqueous solution of 5 percent by weight sodium bicarbonate and withwater. The organic phase is separated off, washed over sodium sulphateand evaporated under reduced pressure. The residual p-[ (4,5 -epoxy-1,S-dimethylhexyl)oxylbenzoic acid propargyl ester is purified'byadsorption of Kieselgel; B.P. -123C/0.05 mmHg.

EXAMPLE 32 By utilizing the procedure of Example 31, 2.0 g of p-[(3,7-dimethyl-2,6-octadienyl)oxy]benzoic acid propargyl ester isconverted into p-[(6,7-epoxy-3,7- dimethyl-Z-octenyl)oxy]benzoic acidpropargyl ester; n 1.5362.

EXAMPLE 33 1.15 g of p-[(3-methyl-2-butenyl)oxy]-a-propargyloxy-tolueneis dissolved in 40 ml of methylene chloride and cooled to 0C. (ice-bathcooling). 1.5 g of 80 percent by weight mchloroperbenzoic acid is addedportionwise to this mixture and the solution is thereafter stirred at 0Cfor 2 hours. The mixture is worked up as follows: diluted with 350 ml ofmethylene chloride; washed with ice-cold 1-N caustic soda; washed withsaturated aqueous sodium chloride solution; dried over sodium sulfate;and evaporated. By chromatography on Kieselgel, there is obtained p-[(2,3-epoxy3 -methylbutyl) oxy]-a-propargyloxytoluene; B.P. 120123C/0.lmmHg.

EXAMPLE 34 6.4 g of 1-[(3-methyl-2-butenyl)oxyl-4-propargyloxy-benzeneis dissolved in 80 ml of methylenechloride and cooled to 0C. (ice-bathcooling). 7.15 g of 80 percent by weight mchloroperbenzoic acid is addedportionwise to this mixture and the solution is thereafter stirred at0C. for 2 hours. The mixture is worked up as follows: diluted with 350ml of methylene chloride; washed with ice-cold l-N caustic soda; washedwith saturated aqueous sodium chloride solution; dried over sodiumsulfate; and evaporated. By chromatography of Kieselgel, there isobtained 1-[(2,3-epoxy-3-methylbutyl)oxy]-4-propargyloxy-benzene; M.P.72-73C.

EXAMPLE 35 By utilizing the procedure of Example 26, by reacting p-[(l,S-dimethylhexyl)thio]benzyl alcohol with propargyl bromide, there isobtained p-[( 1,5-dimethylhexyl)thio]-a-propargyloxy-toluene; n

EXAMPLE 36 By utilizing the procedure of Example 27, p-[(l,5-dimethyl-hexyl)thio]benzoic acid methyl ester is converted into p-[( l,5-dimethylhexyl)thiolbenzyl alcohol; u 1.5270.

EXAMPLE 37 By utilizing the procedure of Example 19, by reacting p-thiobenzoic acid methyl ester with 2-bromo-6- methylheptane, there isobtained p-[( 1,5-dimethylhexyl)-thio]benzoic acid methyl ester; B.P.l68-l70 C/0.5 mml-lg.

EXAMPLE 38 By utilizing the procedure of Example 8, by reacting p-[(,l,S-dimethylhexyl)thio]benzoic acid and propargyl bromide, there isobtained p-[( l ,5-dimethylhexyl)thio] benzoic acid propargyl ester M.P.l30-l 3 lC/0.03 mmHg.

EXAMPLE 39 By utilizing the procedure of Example 24, p-[(1,5-dimethyl-hexyl)thio]benzoic acid methyl ester is converted intop-[(1,5-dimethylhexyl)thiolbenzoic acid; MP. 6365C.

EXAMPLE 40 By utilizing the procedure of Example 8, by reactingp-[(3,6,7-trimethyloctyl)oxy]benzoic acid with propargyl bromide, thereis obtained p-[(3,6,7-trimethyloctyl)oxy]benzoic acid propargyl ester;B.P. l53-l 54 C/0.05 mmHg.

EXAMPLE 41 EXAMPLE 42 Ten g of p-[(l,5-dimethylhexyl)oxy]benzoic acid isheated to 70C. with 20 ml of thionyl chloride for rnlns. The clearyellow-colored solution is evaporated at 50C. under water-jet pumpvacuum. After the addition of 40 ml of propargyl alcohol, the mixture isheated to 70C for min. After evaporation in water-jet pump vacuum, theresidue is chromatographed on Kieselgel, yieldingp-[(l,5-dimethylhexyl)oxy]benzoic acid propargyl ester; RP. 2072l0C/ l.0 mmHg.

EXAMPLE 43 Ten g of p-[(l,S-dimethylhexyl)oxylbenzoic acid methyl ester,30 ml of propargyl alcohol and 0.5 g of sodium methoxide are heated toreflux for one-half an hour. The excess propargyl alcohol is thereuponslowly (5hrs.) 5 off. The residue is poured onto water and extractedwith diethyl ether. The ether solution is dried with sodium sulfate andevaporated. The dark-yellow p-[(l, S-dimethylhexyl)oxylbenzoic acidpropargyl ester obtained is purified over kieselgel.

EXAMPLE 44 Thirteen g of p-[( l ,5-dimethylhexyl)oxy]benzoic acid methylester is heated to reflux with 9 g of propargyl alcohol and 0.1 g ofp-toluenesulphonic' acid. The excess propargyl alcohol is thereuponslowly (5 hrs.) distilled off. The residue is poured onto water andextracted with diethyl ether, The ether phase is dried with sodiumsulfate and evaporated. There is obtained darkyellow p-[( l,S-dimethylhexyl)oxy]benzoic acid propargyl ester which is purified onKieselgel.

The experiments described in the following examples are carried out withthe following representative examples of the propargyloxy derivatives ofthis invention as the active substances.

1. p-[ l ,S-dimethylhexyl)oxy]-a-propargyloxytoluene II. p-[(l,S-dimethylhexyl)oxy]benzoic acid propargyl ester III. p-[( l,5-dimethyl-4-hexenyl)oxy benzoic acid propargyl est er lV.l-[(2,3-epoxy-3-methylbutyl)oxy]benzoic acid propargyl ester l-[( l,5-dimethylhexyl)oxy]-4-(propargyloxy)benzene VI.l-[(2,3-epoxy-3-rnethylbutyl)oxy]-4-(propargyloxy)-benzene.

EXAMPLE 45 Two filter paper discs (24 cm) are sprayed with an acetonicsolution of the active substance, and after drying, the discs togetherwith an untreated paper disc and with a paper disc soaked only withacetone, are each so fixed together that there is formed a tunnel forthe shelter of 10 cockroaches (Blattella germanica) each. Thecockroaches are in the last larval stage. They remain in permanentcontact with the treated paper and are provided with water and food.

The development of the larvae set out is registered daily. 100 percentdisturbance of metamorphosis: A normal animal develops from none of thelarvae Active Amount Number Number Number Activity sub of of of ofstance active larvae normal normal substance images animals I ()"g/cm ll0" 10 l 5 83 Control with l0 l0 acetone Control with 1 0 l 0 acetoneEXAMPLE 46 l A disc of cotton material (10 cm) is sprayed with anacetonic solution of the active substance, and after drying, the disc,together with an untreated disc of material and a disc of materialsoaked only with acetone, are each occupied by 30-60 freshly laid eggsof the meal moth (Ephestia kiihm'ella). The disc is placed in a cage andheld at 25 C. and percent rel. humidity.

The development of the eggs is registered over a few days. percentmortality of the eggs: No development of the embryos in the eggs layedon discs of material soaked with active substance.

Active Amount Number Number Mortality sub of of stance active eggslarvas substance 10*glcm l 10" 32 100 33 0 100 ll 10" 32 0 100 10' 30 0100 Ill 10' 4O 0 100 l O 36 0 100 10 36 O 100 IV l0" 47 O 100 10" 33 0100 V 10" 44 O 100 1O" 34 O 100 Control with 50 50 0 acetone Controlwith 49 46 6 acetone EXAMPLE 47 A disc of woollen material (10 cm) issprayed with an acetonic solution of the active substance, and the disc,together with an untreated disc of material and a disc of materialsoaked only with acetone, are each hung in a cage occupied by 20 youngcloths moth (Tineola biselliella).

The development of the eggs layed at 25C. is registered for 4 days.Hundred percent sterilant action: larvae hatch from none of the eggslaid on treated and untreated discs of woollen material. 100 percentovicidal action: larvae hatch from none of the eggs laid on treateddiscs of woollen material.

Active Amount Sterilant Ovicidal substance of action action active ksubstance 1 0" 0 100 Control with 0 0 acetone Control with 0 0 acetoneEXAMPLE 48 A filter paper strip (90 cm) is sprayed with an acetonicsolution of the active substance and, after drying, the strip, togetherwith an untreated paper strip and a paper strip soaked only withacetone, are each occupied by 3-4 pairs of freshly moulted images of thecotton bug (Dysdercus cingulatus).

The development of the eggs laid daily is registered. 100 percentmortality of the eggs: no development of the embryos in the eggs laid onstrips soaked with active substance.

Active Amount Number Number of Mortality subof of larvae stance activeeggs larvae substance l 0 50 l 00 ll 10 430 100 III 1 0 3 l l 4 99 IV10" 392 60 83 Control with 270 262 3 acetone Control with 4 1 39 5acetone EXAMPLE 49 1 g of p-[(3-methyl-2-butenyl)oxy]-a-( 2-propynyloxy)toluene was dissolved in a mixture of ml of dioxane and 40ml of water. To this solution there was added under cooling with ice10C) portionwise 0.85 g of N-bromosuccinimide. After this addition themixture was stirred at room temperature for 15 hours and then dilutedwith 80 ml of water. Thereafter 2.5 g of sodium sulfite are added andthe solution exhaustively extracted with ether. The combined etherextracts were washed with water, dried over sodium sulfate andevaporated. By chromatography on Kieselgel with hexane/ethyl acetate (8515 parts by volume) there was obtained p-[3-bromo-2-hydroxy-B-methylbutyl )oxy] a-(2-propynyloxy)toluene. n1.5374.

We claim:

1. A compound of the formula:

R1 in wherein R R and R are methyl or ethyl; R and R are hydrogen ormethyl; R, is lower alkynyl; Y and Y are hydrogen, halogen, lower alkylor.lower alkoxy; and m, n and p are integers of from 0 to 1, with atleast one of m n and p being 1.

2. The compound of claim 1 wherein R is propargyl.

3. The compound of claim 2 having the formula:

wherein R R,, R Y and Y' are as above.

4. The compound of claim 3 wherein Y is alkoxy.

5. The compound of claim 3 wherein Y is halogen.

6. The compound of claim 3 wherein said compound isp-[(1,4,5-trimethylhexyl)-oxy] benzoic acid propargyl ester.

7. The compound of claim 4 wherein said compound is 3-methoxy--4-( l,5-dimethylhexyloxy)- benzoic acid propargyl ester.

8. The compound of claim 5 wherein said compound is 4-[( l,5-dimethylhexyl)-oxy]-3-chlorobenzoic acid propargyl ester.

i I i i i

2. The compound of claim 1 wherein R6 is propargyl.
 3. The compound ofclaim 2 having the formula:
 4. The compound of claim 3 wherein Y isalkoxy.
 5. The compound of claim 3 wherein Y is halogen.
 6. The compoundof claim 3 wherein said compound is p-((1,4,5-trimethylhexyl)-oxy)benzoic acid propargyl ester.
 7. The compound of claim 4 wherein saidcompound is 3-methoxy--4-(1,5-dimethylhexyloxy)- benzoic acid propargylester.
 8. The compound of claim 5 wherein said compound is4-((1,5-dimethylhexyl)-oxy)-3-chlorobenzoic acid propargyl ester.